CN103483298A - Method for preparing 5-hydroxymethylfurfural through efficient dehydration of hexose - Google Patents
Method for preparing 5-hydroxymethylfurfural through efficient dehydration of hexose Download PDFInfo
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- CN103483298A CN103483298A CN201310477871.8A CN201310477871A CN103483298A CN 103483298 A CN103483298 A CN 103483298A CN 201310477871 A CN201310477871 A CN 201310477871A CN 103483298 A CN103483298 A CN 103483298A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention relates to a method for preparing 5-hydroxymethylfurfural through efficient dehydration of hexose. The method comprises the steps of in nitrogen, argon or air atmosphere, mixing hexose, graphite oxide and an organic solvent to obtain a reaction system; performing catalytic reaction on the reaction system for 1-6 hours at 50-180 DEG C; neutralizing the reaction solution by using saturated sodium bicarbonate, and filtering, drying and distilling to obtain 5-hydroxymethylfurfural. The method has the advantages that the graphite oxide is used as a catalyst, the price is low, and hexose can be efficiently and highly-selectively catalyzed to prepare 5-hydroxymethylfurfural; the reaction byproduct is water which is small in pollution and environment-friendly and can be treated easily; only renewable compounds including fructose and the like are consumed in the whole process, so that the method is relatively low in cost, can meet requirements of technical economy, has a good application prospect, and is a catalytic reaction system which is wide in application prospect.
Description
Technical field
The present invention relates to the preparation of 5 hydroxymethyl furfural, particularly a kind of method that adopts the hexose high-efficiency dehydration to prepare 5 hydroxymethyl furfural.
Background technology
At present, solve the focus that fossil energy crisis and development low-carbon economy have become global concern, the reproducible biomass of take progressively become the important research direction of chemical field as the raw material production fine chemicals.Wherein, utilize hexose to become one of study hotspot for raw material through the synthetic 5 hydroxymethyl furfural (HMF) of dehydration reaction.Research shows; HMF is the important intermediate of synthetic multiple fine chemicals; as the hardware and software platform compound that connects Wood Adhesives from Biomass and large-scale chemical process; it can react synthesizing new macromolecular material and many high value added products by hydrogenation, oxydehydrogenation, esterification, halogenation, polymerization, hydrolysis and other, is widely used as the numerous areas such as medicine, resene plastics and fuel dope referring to Angew. Chem. Int. Ed. 46 (2007) 7164; Chemical industry progress 5 (2008) 702.In the hexose dehydration generates the process of HMF, catalyst system commonly used comprises mineral acid, solid acid, ionic liquid and metal chloride, wherein, 1) use HCl, H
2sO
4or H
3pO
4deng mineral acid during as catalyzer, generally to add methyl-sulphoxide (DMSO) and polypyrrole alkane ketone (PVP) to make additive, and need in water, mibk/2-butanols two-phase system, be reacted, under this condition, to be transformed into the reaction yield of HMF be 72% left and right in D-Fructose catalysis, referring to Science 312 (2006) 1933 and Green Chem. 9 (2007) 342; U.S. Pat 4740605 has also been reported the method with the Syntheses in water HMF of inorganic acid as catalyst high-temperature catalytic sugar compounds; 2) solid acid catalyst is generally metal phosphate, and when with vanadium phosphorus oxide, made catalyzer, under different condition, to generate the reaction yield of HMF be between 32.9-59.6% in the D-Fructose dehydration, referring to Appl. Catal. A 275 (2004) 111; The process and the purification process thereof that use the synthetic HMF of resin cation (R.C.) Amberlyst 35 catalysis fructose solns have also been reported in patent US7317116 B2; 3) in recent years, the research that ionic liquid directly is used in the fructose dehydration reaction is more, wherein contain some ionic liquids of Methylimidazole ion, and the citric acid special ion liquid that is negatively charged ion can realize the synthetic HMF of effective dehydration of fructose as solvent and catalyzer, referring to J. Mol. Catal. A Chem. 253 (2006) 165; 4) use metal chloride (as CrCl
2) make catalyzer, when solvent is ionic liquid 1-ethyl-3-methylimidazole muriate, the reaction yield that D-Fructose or gluconate dehydratase generate HMF is 70% left and right, referring to Science 316 (2007) 1597.In above-mentioned catalyst system, while with metal chloride, making catalyzer, shortcoming is that catalyzer has larger toxicity, and the price of lyate ion liquid is more expensive; Using the shortcoming of mineral acid or solid acid as catalyst is the catalytic dehydration process that can only be applicable to D-Fructose, and need add a large amount of organic solvents and additive.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, a kind of method that adopts the hexose high-efficiency dehydration to prepare 5 hydroxymethyl furfural is proposed, the method promotes hexose to select dehydration reaction to produce 5 hydroxymethyl furfural with simple solid catalyst graphite oxide, it shows the characteristics of heterogeneous reaction in the catalytic dehydration process, target product selectivity is high, and primary product is easily separated; And catalyst levels can be optimized to trace, be conducive to filtration and the purification of reaction product; Reaction system is simple, and aftertreatment is easy; Production cost is lower, and safety is without hidden danger, also friendly to environment.
Technical scheme of the present invention:
A kind of method that adopts the hexose high-efficiency dehydration to prepare 5 hydroxymethyl furfural, take hexose as raw material, take graphite oxide as catalyzer, high catalytic performance and its special polar group structure effect by graphite oxide, optionally the catalysis hexose is sloughed three water moleculess, thereby realized the clean synthetic of 5 hydroxymethyl furfural, concrete grammar is: in nitrogen, argon gas or air atmosphere, hexose, graphite oxide and organic solvent are mixed to get to reaction system; Reaction system is carried out to catalyzed reaction under temperature 50-180 ℃, and the reaction times is 1-6 hour; With saturated sodium bicarbonate neutralization reaction solution, after filtration, drying, distillation, can make 5 hydroxymethyl furfural.
The mass ratio of described hexose, graphite oxide and organic solvent is 1:0.0001-0.4:2-50.
Described hexose is fructose or glucose.
Described graphite oxide is obtained through Hummers method or oxidation style by compact crystal shape graphite, crystalline flake graphite or hidden matter spar China ink.
Described organic solvent is acetonitrile, cyanobenzene, ethyl acetate, methyl acetate, chloroform, monochloro methane, benzene, chlorobenzene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone or tetrahydrofuran (THF)-water, methylene dichloride-water two-phase mixture.
Advantage of the present invention is: take graphite oxide as catalyzer cheap, but high-level efficiency, highly selective catalysis hexose prepare 5 hydroxymethyl furfural; Byproduct of reaction is water, pollute little, environmental friendliness, product is processed well; The renewable compounds such as just fructose that whole process consumes, cost is lower, can meet the requirement of Technological Economy, and good application prospect is arranged, and is a catalystic converter system had wide application prospects.
Embodiment
Give further instruction below by example to the present invention.
embodiment 1: the catalytic dehydration of fructose
By 1.0g(5.6mmol) fructose is dissolved in the 10mL dimethyl sulfoxide (DMSO), add 0. 01g graphite oxide, this graphite oxide is obtained through the Hummers method by compact crystal shape graphite, at 120 ℃, under nitrogen protection, the magnetic agitation reaction is after 4 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose is 79%, and the yield of 5 hydroxymethyl furfural can reach 60.8%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 2: the catalytic dehydration of fructose
By 1.0g(5.6mmol) fructose is dissolved in 10mL N; in dinethylformamide; add the 0.05g graphite oxide; this graphite oxide is obtained through oxidation style by compact crystal shape graphite; at 140 ℃; under argon shield, the magnetic agitation reaction is after 2 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result.The fructose transformation efficiency is 69%, and the yield of 5 hydroxymethyl furfural can reach 47%; With after saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 3: the catalytic dehydration of fructose
By 1.0g(5.6mmol) fructose is dissolved in 10mL N, in the N-N,N-DIMETHYLACETAMIDE, add 0.075 g graphite oxide, this graphite oxide is obtained through the Hummers method by crystalline flake graphite, at 100 ℃, under nitrogen protection, the magnetic agitation reaction is after 4 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The fructose transformation efficiency is 54%, and the yield of product 5 hydroxymethyl furfural can reach 41%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 4: the catalytic dehydration of fructose
By 1.0g(5.6mmol) fructose is dissolved in 10 mL high purity waters, add 0.2 g graphite oxide, this graphite oxide is obtained through oxidation style by crystalline flake graphite or hidden matter spar China ink, at 120 ℃, under air atmosphere, the magnetic agitation reaction is after 4 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose is 52%, and the yield of 5 hydroxymethyl furfural can reach 3.9%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 5: the catalytic dehydration of fructose
By 1.0g(5.6mmol) fructose is dissolved in 10mL N-Methyl pyrrolidone system, add 0.15 g graphite oxide, this graphite oxide is obtained through the Hummers method by hidden matter spar China ink, at 160 ℃, under nitrogen protection, the magnetic agitation reaction is after 1 hour, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The yield that the transformation efficiency of fructose is 74%, 5-hydroxymethylfurans aldehyde can reach 57%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 6: the catalytic dehydration of fructose
By 1.0g(5.6mmol) glucose is dissolved in 10mL methylene dichloride-water (1:1, v/v) in, add the 0.1g graphite oxide, this graphite oxide is obtained through oxidation style by hidden matter spar China ink, at 110 ℃, under argon shield, the magnetic agitation reaction is after 5 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The yield that inversion rate of glucose is 64%, 5-hydroxymethylfurans aldehyde can reach 46. 8%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 7: the catalytic dehydration of fructose
By 1.0g(5.6mmol) glucose is dissolved in 10mL tetrahydrofuran (THF)-water, add 0.1 g graphite oxide, this graphite oxide is obtained through the Hummers method by compact crystal shape graphite, at 180 ℃, under nitrogen protection, the magnetic agitation reaction is after 2 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of glucose can reach the yield 58.3% of 82%, 5-hydroxymethylfurans aldehyde; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 8: the catalytic dehydration of glucose
By 1.0g(5.6mmol) glucose is dissolved in 10mL N, in N-N,N-DIMETHYLACETAMIDE system, add 0.125 g graphite oxide, this graphite oxide is obtained through oxidation style by compact crystal shape graphite, at 140 ℃, under air atmosphere, the magnetic agitation reaction is after 5 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; Inversion rate of glucose can reach 69%, and the yield of product 5 hydroxymethyl furfural can reach 6.5%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
embodiment 9: the catalytic dehydration of glucose
By 1.0g(5.6mmol) glucose is dissolved in the 10mL dimethyl sulfoxide (DMSO), add 0.175 g graphite oxide, this graphite oxide is obtained through oxidation style by crystalline flake graphite or hidden matter spar China ink, at 120 ℃, under air atmosphere, the magnetic agitation reaction is after 4 hours, with gas chromatograph-mass spectrometer (GC-MS) and efficient liquid phase chromatographic analysis reaction result; The yield that the transformation efficiency of glucose can reach 67%, 5-hydroxymethylfurans aldehyde is 4.1%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, distillation, collect product.
Above-mentioned example shows, the novel organic catalyst system provided in the present invention is provided, and in suitable reaction medium, the condition provided according to invention, can high-level efficiency, highly selective generates 5 hydroxymethyl furfural by the hexose catalytic dehydration.Reaction can be carried out under nitrogen protection or in air atmosphere; In reaction process, catalyzer is insoluble to reaction system, embody advantage and the effect of heterogeneous catalyst fully, thereby selectivity of product is high; After whole reaction, catalyzer can filter and separate with substrate and product, is easy to separate.In total reaction process, just fructose and the glucose compounds that consume; Production cost, cheap, product is mainly heterogeneous ring compound, more friendly to environment.Reaction process is simple, can meet the requirement of Technological Economy, is the catalyst system with broad prospect of application.
Claims (5)
1. a method that adopts the hexose high-efficiency dehydration to prepare 5 hydroxymethyl furfural, it is characterized in that: take hexose as raw material, take graphite oxide as catalyzer, high catalytic performance and its special polar group structure effect by graphite oxide, optionally the catalysis hexose is sloughed three water moleculess, thereby realized the clean synthetic of 5 hydroxymethyl furfural, concrete grammar is: in nitrogen, argon gas or air atmosphere, hexose, graphite oxide and organic solvent are mixed to get to reaction system; Reaction system is carried out to catalyzed reaction under temperature 50-180 ℃, and the reaction times is 1-6 hour; With saturated sodium bicarbonate neutralization reaction solution, after filtration, drying, distillation, can make 5 hydroxymethyl furfural.
2. adopt according to claim 1 the hexose high-efficiency dehydration to prepare the method for 5 hydroxymethyl furfural, it is characterized in that: the mass ratio of described hexose, graphite oxide and organic solvent is 1:0.0001-0.4:2-50.
3. adopt according to claim 1 the hexose high-efficiency dehydration to prepare the method for 5 hydroxymethyl furfural, it is characterized in that: described hexose is fructose or glucose.
4. adopt according to claim 1 the hexose high-efficiency dehydration to prepare the method for 5 hydroxymethyl furfural, it is characterized in that: described graphite oxide is obtained through Hummers method or oxidation style by compact crystal shape graphite, crystalline flake graphite or hidden matter spar China ink.
5. adopt according to claim 1 the hexose high-efficiency dehydration to prepare the method for 5 hydroxymethyl furfural, it is characterized in that: described organic solvent is acetonitrile, cyanobenzene, ethyl acetate, methyl acetate, chloroform, monochloro methane, benzene, chlorobenzene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone or tetrahydrofuran (THF)-water, methylene dichloride-water two-phase mixture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725337A (en) * | 2015-03-06 | 2015-06-24 | 四川大学 | Method for synthesizing 5-hydroxymethylfurfural through carbon dioxide promoted carbohydrate |
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| CN102212048A (en) * | 2011-04-19 | 2011-10-12 | 天津理工大学 | Method for preparing hydroxymethyl furfural by catalytic dehydration reaction of hexose |
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| EP2647631A1 (en) * | 2010-11-29 | 2013-10-09 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Preparation method of catalyzing carbohydrate into 5-hydroxymethylfurfural |
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Patent Citations (5)
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| US20100113764A1 (en) * | 2008-11-05 | 2010-05-06 | Blair Richard G | Solid Acid Catalyzed Hydrolysis of Cellulosic Materials |
| CN101811066A (en) * | 2010-05-14 | 2010-08-25 | 天津大学 | Catalyst for synthesizing 5-hydroxymethylfurfural by hexose dehydration and method for synthesizing 5-hydroxymethylfurfural |
| EP2647631A1 (en) * | 2010-11-29 | 2013-10-09 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Preparation method of catalyzing carbohydrate into 5-hydroxymethylfurfural |
| CN102212048A (en) * | 2011-04-19 | 2011-10-12 | 天津理工大学 | Method for preparing hydroxymethyl furfural by catalytic dehydration reaction of hexose |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725337A (en) * | 2015-03-06 | 2015-06-24 | 四川大学 | Method for synthesizing 5-hydroxymethylfurfural through carbon dioxide promoted carbohydrate |
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